Symmetrical disazo dyes containing phthalimido groups



United States Patent Ofice US. Cl. 260-152 12 Claims ABSTRACT OF THE DISCLOSURE 3,513,153 Patented May 19, 1970 in which the radicals R represent a member selected from the class consisting of naphthy], phenyl and phenyl substituted with one to three substituents selected from the group consisting of chloro, nitro, methyl, methoxy, ethoxy, acetylamino and benzoylamino; X represents a member selected from the group consisting of nitro, chloro, bromo, fluoro, lower alkyl, lower alkoxy, trifluoromethyl, phenylsulphonyl, methylsulphonyl, ethylsulphonyl, carbo methoxy and carbo ethoxy; m stands for an integer from to 3; and A represents a member selected from the group consisting of phenylene, substituted phenylene, wherein the substituents are 1 to 4 members selected from the group consisting of chloro, methyl, methoxy, ethoxy,

and nitro; diphenylene; substituted diphenylene wherein Azo dyestuffs free from sulfonic acid groups which the substituents are selected from the group consisting of correspond to the formula R-NH-OG OH in which the radicals R represent aromatic radicals; X chloro, methyl, methoxy, ethoxy, and nitro; cyclohexylene; stands for substituents; m is 0 to 3; and A is a carbocyclic naphthylene and the divalent radicals or heterocyclic radical. These dyestuffs are valuable pig- B l O- $011 ment dyestuffs predominantly in the yellow-to-bluish-red range, and they are resistant to deterioration by solvent,

light, or heat when incorporated in plastics, lacquers, and papers.

DISCLOSURE The object of the present invention is toprovide a process for the production of valuable new azo dyestuffs which are free from sulphonic acid groups and correspond to the general formula I )m O (I) (X) m I 1% 00m wherein B is selected from the group consisting of hydrogen, chloro, and methoxy The radicals R may be monoor polynuclear, those of the benzene and naphthalene series being preferred. 75

Examples are the following radicals: phenyl; 2- or 3- 0r 4- methylphenyl-l; 2- or 3- or 4-chl0rophenyl-1; 2- or 3- or 4-methoxyphenyl-1; 4-ethoxyphenyl-l; Z-methyl-S-chlorophenyl-l; 2-methyl-4-methoxyphenyl-1; naphthyl-l or -2; 3-nitrophenyl-1; 2,4-dimethylphenyl-1; 2,4-dimethoxy-5- chlorophenyl- 1; 2,5 -dimethoxy-4-chlorophenyl- 1; 2-methyl-4-chl0r0phenyl-1 and 2,5-dimethoxy-pheny1-1, 4-acetylaminophenyl-l; 4-benzoylamino-phenyl-1; 2-ethoxyphenyl- 1; 2,3-dimethylphenyl-1; 3,5-dimethyl-phenyl-1; 2-methoxy-5-chlorophenyl- 1 Suitable substituents X are, for example: lower alkyl substituents, such as methyl and ethyl; chloro and nitro substituents; lower alkoxy substituents, such as methoxy and ethoxy; fluoro, bromo, methylsulphonyl, ethylsulphony], phenylsulphonyl, trifiuoromethyl substituents; and carbalkoxy substituents, such as carbomethoxy and carbethoxy.

The carbocyclic radical A is unsaturated or saturated and may be monoor polynuclear. In the case of polynuclear radicals these may be fused or linked with one another by simple carbon-carbon bonds or also by aliphatic or other bridge members. Examples of suitable bivalent radicals A are:

-@ 4&

llzN '61 CH3 N02 IC1 Cl Q} 6H H OCH; SCH;

H CH C1 C1 OCH;

{DU-Q1 A group of especially valuable dyestuffs in the range of the products of the Formula I corresponds to the formula in which R stands for hydrogen or for methyl, chloro, nitro, methoxy and ethoxy substituents, R for hydrogen or for methyl chloro and methoxy substituents, and R for hydrogen or chloro substituents, while A has the same meaning as above.

are, in particular, 2- or 3- or 4-methylor chloroor methoXyphenyl-l; 2- or 4-ethoxyphenyl-l; 2-methyl-3- chloroor 2-methyl-4-chlorophenyl-1; 2,5-dichlorophenyll; 2,4-dimethyl-phenyl-l; and naphthyl-l or -2. The following are preferred azo dyestuffs which are free from sulfonic acid groups and correspond to the formula in which R stands for hydrogen or chloro, methyl, nitro, methoxy, or ethoxy; R stands for hydrogen, or chloro, methyl, or methoxy; R stands for hydrogen or chloro; and A represents a member selected from the group consisting of phenylene, substituted phenylene, wherein the substituents are 1 to 4 members selected from the group consisting of chloro, methyl, methoxy, ethoxy, and nitro; diphenylene; substituted diphenylene wherein the substituents are selected from the group consisting of chloro, methyl, methoxy, ethoxy and nitro; cyclohexylene; naphthylene and the divalent radicals aurora-Q- wherein B is selected from the group consisting of hydrogen, chloro, and methoxy til It w O ll 0/ 1 I H2 H H i I CH {j/ F? K N N rj l/N N\@/S\ 1 N /N I] Q s N s s N H NC Cw 343 N-N Q Q The process for the production of the new azo dyestuffs of the Formulae I and la consists in that azo compounds of the formula and 0 O OH C O OH in which R, X and m have the same meaning as above, or azo compounds of the formula NHO O OH COOH COOII (Ila) H NANH in which A has the same meaning as above,

(III) in a molar ratio of components (II) or (11a) to component (III) of approximately 2:1 in the presence of acidic condensation agents and that the components are so chosen that the final dyestuifs are free from sulphonic acid groups. The reaction of the starting components is preferably carried out in a high-boiling organic solvent or solvent mixture, but the components themselves can also serve as organic solvents. The condensation takes place at an elevated temperature, generally in the range from C. to 240 C., preferable between C. and 180 C.

The monoazo dyestuffs (II) and (Ila) are obtained in the usual manner by diazotising the optionally substitued aminophthalic acids or their functional derivatives and coupling with 2-hydroxy-naphthoic acid-3-arylides, the components being free from sulphonic acid 'groups. The following diazo components can be used for this purpose, for example: 3-amino-phthalic acid; 3-amino-phthalic acid monoand diesters, such as 3-amino-phthalic acid monomethyl ester-10 or 3-aminophthalic acid dimethyl ester; 3-aminophthalimide; 3amino-6-methyl-phthalic acid; 3- amino-4-methyl-phthalic acid; 3amino-S-methyl-phthalic acid; 3amino-S-nitro-phthalic acid; 3-amino-6-nitrophthalic acid; 3-amino5-rnethoxy-phthalic acid; 3-amino- 4-methoxy-phthalic acid; 3 amino-6-methoxy-phthalic acid; 3amino-6-chloro-phthalic acid; 3-amino-4-chlorophthalic acid; 3-amino-6-bromo-phthalic acid; 3-amino-6- fluoro-phthalic acid; 3amino-5,6-dimethoxy-phthalic acid; 3-amino-6-cyano-phthalic acid; 3-amino-5-methoxy-6- ethoxy-phthalic acid; 3arnino-6methylsulphonyl-phthalic acid; 3amino6trifluoromethyl-phthalic acid; 3-amino-5- carbethoxy-phthalic acid; 3amino-6-carbethoxy-phthalic acid.

The following coupling components can be used, for example:

Z-hydroxy-naphthoic acid- (3 )-anilide; 2-hydroXy-naphthoic acid-( 2) (o-anisidide) Z-hydroxy-naphthoic acid- (3 (p-anisidide) Z-hydroxy-naphthoic acid- (3 (o-toluidide Z-hydroxy-naphthoic acid-( 3 (p-toluidide); 2-hydroxy-naphthoic acid-( 3 3'-nitroanilide) 2-hydroxy-naphthoic acid-( 3 2,4'-dimethyl) anilide; 2-hydroXy-naphthoic acid-( 3 (2'-chloro)-anilide; Z-hydroxy-naphthoic acid- (3 (4'-chloro) anilide; 2-hydroxy-naphthoic acid- (3 2-methyl- 5'-.chloro) anilide; 2-hydroxy-naphthoic acid- (3 (2',4"dimethoxy- 5-ch1oro) anilide; Z-hydroxy-naphthoic acid- (3 )-(2,5'-dimethoxy- 4'-chloro) anilide; 2-hydroxy-naphthoic acid- 3 2-methyl- 4-chloro) anilide; 2-hydroxy-naphthoic acid-(3 -(2'-methyl- 4-methoxy anilide; 2-hydroxy-naphthoic acid- (3 [naphthyl l amide; 2-hydroxy-naphthoic acid-( 3 [naphthyl(2')-]-amide; 2-hydroxy-naphth0ic acid-( 3 -(2',5-dimethoxy) anilide; 2-hydroxy-naphthoic acid-( 3 )-(4-ethoxy) anilide. 2-hydr0xy-naphthoic acid- 3 -(4'-acety1amino) anilide; Z-hydroxy-naphthoic acid-( 3 (4'-benzoylamino)anilide; Z-hydroxy-naphthoic acid- 3 -(2-ethoxy anilide; 2-hydroXy-n aphthoic acid- 3 2,3 '-dimethyl anilide; Z-hydroxy-naphthoic- (3 (2'-methoxy- -chloro) anilide.

The alkyl, aryl, aralkyl monoand diesters and the anhydrides or imides of the above substituted phthalic acids can also be used. Compared with the free dicarboxylic acids, the esters are frequently more readily soluble in the high-boiling organic solvent used for the condensation.

The following diamines (III) can be used, for example, for the condensation of the azo compounds according to the invention:

1,4-diamino-2-chloro-benzene; 1,4-diamino-Z-methyl-benzene; 1,4-diamino-2,S-dimethyl-benzene; 1,4-diamino-2-nitro-benzene; 1,4-diarnino-2-methyl-S-methoxy-benzene; 1,4-diamino-Z-methoxy-benzene;

,4 diarnino-Z,S-diethoxy-benzene; -diamino-benzene;

-diamino-4-methyl-benzene; -diamino-4-chloro-benzene; -diamino-4-rnethoxy-benzene;

diamino-4-methyl-6-nitro-benzene; -diamino-2,4,5,6-tetrachloro-benzene; ,4-diamino-2,3,5,6-tetrachloro-benzene; 1,2-diamino-benzene; 1,2-diamino4-nitro-benzene; 1,3-diamino-2-methyl-benzene; 1,4-diamino-benzene; 4,4-diarnino-2,2'-dichloro-diphenyl; 4,4'-diamino-3,3-dichloroor -3,3'-dimethylor -3,3-dimethoxy-diphenyl; 4,4-diamino-2-nitro-diphenyl; 4,4-diamino-3-methyl-diphenyl; 4,4-dia mino3,3-diethoxy-diphenyl; 4,4-diamino-2,2-di-methyl-diphenyl; 4,4-diarnino-3,3-dimethyl-6,6'-dinitro-diphenyl; 4,4-diamino-2,2'-dichloro-5,5'-dimethoxy-diphenyl; 4,4-diamino2,2,5,5-tetrachloro-diphenyl; 4,4'-diamino-3,3'5,5'-tetramethyl-diphenyl; 4,4'-diamino-octachloro-diphenyl; 4,4-diamino-diphenyl ether; 4,4-diamino-diphenyl-sulphone; 3,3-diamino-4,4-dichloro-diphenylsulphone; 3,3'-diamino-4,4-dimethoxy-diphenylsulphone; hexahydro-phenylene-diamine-1,4; hexahydro-phenylene-diamine-l,3; 4,4-dia-mino-diphenyl-ketone; 3,3-diamino-diphenyl-ketone; 3,3-diamino-4,4-dichloro-dipheny1-ketone; 4,4-diamino-diphenyl-methane; 4,4-diamino-di'benzyl; 3,3'-diamino-diphenyl-methane; 4,4-diamino-3,3',5,5'-tetrachloro-diphenyl-methane; 4,4'-diamino-stilbene; 4,4-diamino-benzanilide; 2,8-diamino-chrysene,1,4-diamino-naphthalene; 2,7-diamino-naphthalene; 2,6-diamino-naphthalene; 2,6-diamino-pyridine; 3,6-diamino-pyrazine; 2,6-diamino-benzothiazole; 2-(4amino-phenyl)-5-amino-benzothiazole; 2,5-bis- (4-aminophenyl) -oxodiazole; 4,4'-diamino-diphenyl-urea; 4,4-diamino-3,3'-dirnethoxy-stilbene; 2- (4-aminophenyl -6-amino-benzothiazole; 2,7-diamino-fluorene; 2,7-diamino-diphenylene-oxide; 2,7-diamino-diphenylene-sulphone; 2,5-bis-(4-aminophenyl)-thiadiazole; 2,6-bis- (4-aminophenyl) -triazole; l,4-diamino-anthraquinone; 1,5-diamino-anthraquinone; 2,6-diamino-pyrimidine; 4,4-diamino-diphenyl.

The following solvents boiling above 80 C. can be used, for example, for the condensation of the monoazo dyestuffs (II) or (Ila) with the diamines (III) in highboiling organic solvents; benzene, toluene, xylenes, chlorobenzenes, nitro'benzene, quinoline, glacial acetic acid, cyclohexane, 1,2,3,4-tetrahydronaphthalene, naphthalene,

tetrachloroethylene, di-n-butyl ether, anisole, diphenyl ether, decalin and mixtures of such solvents.

Suitable acidic condensation agents are, for example: acetic acid, propionic acid, anhydrous sodium acetate, zinc chloride, ferric chloride, aluminum chloride, hydrochloric acid, sulphuric acid, oxalic acid, formic acid, boron trifluoride and orthophosphoric acid.

The reaction of the dicarboxy-azo compounds (II) 01' (Ha) or of their functional derivatives with the diamino components (III) is carried out in a ratio of approximately 2:1. A slight excess of components (II) of (Ha) is frequently desirable, in order to react the components (III) completely.

Symmetrical or asymmetrical dyestuffs of the formula (I) can be synthetised, depending on the choice of the components (II) or (11a).

The products obtained according to the present process are valuable pigment dyestuffs the shades of which are predominantly in the yellow to bluish-red range. The dyestuffs are sometimes obtained in the amorphous state, but usually in crystalline form and in good yields. They are characterised by good fastness to solvents, light and migration and by good thermal stability and are preferably used for the colouring of plastics, such as polyvinyl chloride containing plasticisers, and copolymers or grafted polymers of acrylonitrile-butadiene-styrene, of lacquers and papers and for the production of printing inks and pigment pastes.

Belgian patent specification No. 652,251 already describes pigment dyestuffs of the general formula in which K is defined as the radical of any coupling component, A is an aromatic or heterocyclic system and R as a bivalent alkyl, aryl, aralkyl or hetero radical.

However, this patent specification does not contain a single example of a dyestuff of the general formula there indicated, and not even an example of only one of the components K, A and R The patent specification otherwise only contains a few, very general data regarding processes for the production of the pigment dyestuffs.

The following examples are given for the purpose of illustrating the invention; the parts are parts by weight and the temperatures are given in degrees centrigrade.

EXAMPLE 1 65 parts 3-amino-phthalic acid are dissolved in 600 parts dilute hydrochloric acid (5:1) and diazotised at 05 with a solution of 25 parts sodium nitrite in 100 parts water. The excess nitrite is destroyed by means of amidosulphonic acid.

The diazo suspension is introduced into a solution of 100 parts 2-hydroxy-naphthoic acid-(3)-2-toluidide in 700 parts ethanol, to which a solution of 100 parts caustic soda in 200 parts Water has been added and which is cooled to 510. The reaction mixture is subsequently further stirred at 1015 for 4 hours, adjusted to pH 1-2 by the addition of 10% hydrochloric acid, washed with Water until free from acid, and dried at 160 parts monoazo-o-dicarboxylic acid are thus obtained.

9.8 parts of this dyestuif are suspended in 500 parts o-dichlorobenzene, 50 parts glacial acetic acid are added and the reaction mixture is heated at 120 for 2 hours. 1.22 parts 1,4-diamino-2-methyl-benzene are then added and heating is continued at -140" for 1012 hours. The pigment is isolated at 5060, washed with 100 parts o-dichlorobenzene at 50 in 4 portions and dried in a vacuum at 80 until the weight is constant.

7.6 parts of the red disazo pigment of the formula EXAMPLE 2 are thus obtained.

1 9.80 parts of the azo dyestuff prepared from diazotised are obtained. The pigment is characterised by a very good fastness to light. Its fastness to lacquer coating at 130 is also very good.

EXAMPLE 3 9.60 parts of the monoazo dyestuff prepared from diazotised 3-amino-phthalic acid and 2-hydroxy-naphth0ic acid-(3)-anilide are suspended in 250 parts chlorobenzene, 25 parts glacial acetic acid are added and the reaction mixture is heated at 100 C. for 1 hour. 1.58 parts 2,7-diamino-naphthalene are then added and heating is continued at 120 for -12 hours. The pigment is filtered off with suction at about 50, washed with 50 parts chlorobenzene at 50 and dried in a vacuum at 80. 8.25 parts of the red pigment dyestufi of the formula NH OC o are obtained.

12 EXAMPLE 4 44.5 parts 3-amino-phthalic acid are suspended in 500 parts water, 250 parts ice and parts concentrated hydrochloric acid are added and the mixture is diazotised at 0-5 with a solution of 17.2 parts sodium nitrile in parts Water. The excess nitrite is destroyed by means of amidosulphonic acid.

74 parts 2-hydroxy-naphthoic acid-(3)-4'-chloroanilide are suspended in 200 parts ethanol, 400 parts of a 10% sodium hydroxide solution are added and the above diazo suspension is introduced in portions at 5-10. As soon as the coupling is completed, the reaction mixture is acidified with semi-concentrated hydrochloric acid, the dyestuif is filtered 01f with suction, washed with water until 5 neutral and dried at 80. 106 parts of monoazo compound are obtained. 10.3 parts of the monoazo compound so obtained are heated in 250 parts o-dichlorobenzene and 25 parts glacial acetic acid at 100 for 2 hours. 1.14 parts hexahydro-phenylene-diamine-1,4 are then added and the mixture is kept at -140 for a further 20 hours. The precipitated pigment is filtered 01f with suction at 40, washed with warm o-dichlorobenzene and light petrol and dried at 60 until the Weight is constant. 9.2 parts of the brilliant red diazo dyestuff of the formula are obtained.

EXAMPLE 5 10.3 parts of the monoazo dyestutf prepared from 3- amino-phthalic acid and Z-hydroxy-naphthoic acid-(3)-4'- chloroanilide are heated in 50 parts o-dichlorobenzene and 50 parts glacialacetic acid at 120 for 4 hours. 1.97 parts 3,6-diamino-carbazole are then added and the reaction mixture is kept at for a further 10 hours. The precipitated pigment is filtered off with suction, washed with parts o-dichloro-benzene at 50 and dried in a vacuum at 80. 10.6 parts of the deep red pigment dyestulf of the formula H0 CONH- -o1 are obtained.

EXAMPLE 6 90 parts 3-amino-phthalic acid are suspended in 1000 parts water, 500 parts ice and 162 parts concentrated hydrochloric acid are added and the mixture isdiazotised 13 at -5 with a solution of 34.5 parts sodium nitrile in 200 parts water.

154 parts 2 hydroxy-naphthoic acid-(3)-4-ethoxyanilide are suspended in 300 parts alcohol, a solution of 80 parts caustic soda in 200 parts Water is added, 500 parts ice are thrown in and the above diazo suspension is then introduced in portions at 510. When the coupling is completed, the reaction mixture is acidified with semiconcentrated hydrochloric acid, the product is filtered off with suction, washed with water until neutral and dried at 80. The yield of monoazo dyestufi is 218 parts. The dyestulf is converted into the anhydride by heating it in 1000 parts chlorobenzene with 100 parts acetic anhydride at about 100 for 2 hours. The product is filtered off with suction, washed with light petrol, dried at 80, and 179 carts monoazo-o-dicarboxylic anhydride of M.P. 296- 298 are thus obtained.

10.0 parts of the anhydride and 2.0 parts 4,4-diaminodiphenyl ether are heated in 500 parts o-dichlorobenzene and 50 parts glacial acetic acid at 130140 for 12 hours, the pigment is subsequently filtered off with suction at 60, washed with warm o-dichlorobenzene and dried in a.vacuum at 80. The yield of pigment of the formula is 10.8 parts. The product has good fastness to light and lacquer coating. EXAMPLE 7 10.5 parts of the azo dyestuff prepared from 3-aminophthalic acid and 2-hydroxy-naphthoic acid-(3)-4-ethoxyanilide are heated in 500 parts chlorobenzene with 50 parts aceticacid at 100 for 3'hours. 222- parts of the diamino-benzo-bis-thiazole of the formula are thenadded and heating is continued at 130 for 12 hours The precipitated pigment is filtered off with suction at washed with parts chlorobenzene at 50 and subsequently with 200 parts light petrol, and dried. The yieldis 11.1 parts of the red pigment of the following formula:

EXAMPLE 8 10-l5. The reaction mixture is stirred at room temperature for 1-2 hours, adjusted to pH 2 by means of semi-concentrated by hydrochloric acid, the dyestui'f is filtered off with suction, washed with water until neutral adn dried at 80. The yield is 46 parts monoazo dyestufli.

10.9 parts of this monoazo dyestuff are heated in 200 parts o-dichlorobenzene and 20 parts glacial acetic acid at for 4 hours, 2.12 parts 4,4-diamino-dibenzyl are then added and the reaction mixture is kept at for 20 hours. The precipitated pigment is filtered off with suction at 50, washed with o-dichlorobenzene at 50 and dried in a vacuum at 80 until the weight is constant. Yield: 10.2 parts of the disazo pigment of the formula EXAMPLE 9 21 parts 3-amino-6 methoxy-phthalic acid are suspended in 250 parts water, parts ice and 35 parts concentrated hydrochloric acid are added, and the mixture is diazotised at 05 with a solution of 7.0 parts sodium nitrite in 40 parts water.

30 parts 2-hydroxy-naphthoic acid-(3)-2'-methoxyanilide are suspended in 40 parts ethanol, parts of a 10% sodium hydroxide solution and 100 parts ice are added, and the above diazo suspension is introduced in portions at 5-10. The reaction mixture is subsequently stirred at room temperature for 2 hours, acidified with hydrochloric acid (1:1), the dyestuff is filtered off with suction, washed with water until neutral and dried. Yield: 45 parts monoazo dyestuif.

10.8 parts of this dyestuif are heated in 250 parts chlorobenzene and 25 parts glacial acetic acid at 110 for 2 hours, 1.22 parts 1,3--diamino-2-methy1-benzene are added and the reaction mixture is kept at 125 for a further 10 hours. The precipitated product is filtered oil with suction at 40, washed with 100 parts chlorobenzene at 40 and dried in a vacuum at 60 until the weight is 3,513,153 15 16 constant. 9.4 parts of the pigment dyestuif of the foradded and the reaction mixture is kept at 120 for a mula further 12 hours. The product is filtered off with suction at 50, washed with 100 parts tetralin at 50 and dried in a vacuum at 80 until the weight is constant. 10.2 parts of the disazo dyestuif of the formula OOHz C1 N=N O N=N O )1 -1 CHa l N U l 43 -1.

are obtained. are obtained.

EXAMPLE 11 11.4 parts of the azo dyestulf prepared from diazotised EXAMPLE 1o 3-amino-4-ch1oro-phthalic acid and Z-hydroxy-naphthoic acid-(3)-[naphthyl-(1)]-amide are heated in 500 parts o-dichloro-benzene and 50 parts glacial acetic acid at 120 for 2 hours, 2.42 parts 4,4-diamino-diphenyl-urea are added and the reaction mixture is kept at 130-140 for a further 15 hours. The precipitated pigment dyestuif is filtered 0E with suction at washed with warm o-dichlorobenzcne and dried in a vacuum at Yield: 11.1 parts of the dyestufi of the formula Valuable red pigment dyestuffs are also obtained, when the methods described in the above examples are applied but, instead of the diazo components, coupling components and diamines there mentioned, the diazo and counaphthoic acid-(3)-2'-chloroanilide are heated in 500 45 pling components and the diamines specified in the folparts tetralin and 50 parts propionic acid at for 3 lowing table are employed, the 3-amino-phthalic acid being hours. 2.12 parts 4,4'-diamino-azobenzene are then used in the form of the free acids or of the anhydrides:

10.9 parts of the monoazo dyestulf prepared from diazotised 3-amino-6-methyl-phthalic acid and 2-hydroxy- Diazo component Coupling component Diamine 3-arnlno-phthalic acid Z-hydroxy-naphthoic acid-(3)-ani1lde 4,4-diamino-diphenyl-methane. Do do 4,4-diamino-diphenyl ether. D0 .d0 1,4-diamin0-hexahydrobenzene. Do do 1,3-diamino-2-methyl-benzene. Do do 4,4'-diamino-dipheny1-urea. Do 2-hydroxy-naphthoic acid-(3)-2-to1uidide.. 4,4-diamino-diphenyl ether. D do 4,4-diarnino-dibenzyl. D 1,4-diamino-hexahydrobenzene. Do do 4,4-diamino-diphenyl-urea. Dodo 4,4'-dia.min0-benzanilide. Do do 2,7-diamino-naphthalene. Do Z-hydroxy-naphthoic acid-(3)-4-chloro-anilide 1,4-diamino-2-rnethyl-benzene. D do 1,3-dlamino-benzene.

1,3-diamino-2rmethyl-benzene. 4,4'-diamino-dlphenyl-methane.

4,4-diamino-diphenyl ether. 4,4-diamino-diphenylsulphone. 2,7-diamino-naphthalene. 1,8-dlamino-benzene.

1,3-diamino-2-methyl-benzene- 1,4-diamino-hexahydro-benzcne. 4,4-diamino-sti1bene.

4,4'-diamino-diphenyl-urea. 4,4-diamino-azobenzene. 4,4-diamino-diphenyl ether. 4,4-diamlno-diphenyl thioether.

4,4-diamino-diphenylsulphone. 4,4'-diamino-diphenyl-methane. 4,4-diamino-benzanilide.

Do D do 4,4-diamino-diphenyl-urea. S-aminofi-methoxy-phthalic acid Z-hydroxy-naphthoic acid-(3)-anilide 1,3-diamino-benzene.

D n 4,4-diamino-diphenyl-sulphone. D do 4,4-diamino-diphenyl-methane.

.... 2,7-diamino-naphthalene.

do 4,4-diamino-diphenyl ether.

D0 do 4,4-diamino-diphenyl ether.

D0 ..do 2,7-diamino-diphenylene-oxlde.

- 2-hydroxy-naphthoic acid- (3) 4 -ehlor0anilide.

1,3-diamino-2-methyl-benzene.

Diazo component Coupling component Diamine D .110 4,4diarnino-diphenyl-methane.

4,4 diarnino-diphenyl ether.

2,7-diarnino-naphthalene. 1A-diarnino-hexahydrobenzene. 2,7-diarninonaphthalene. 4,4-diarnino-diphenyl-methane. 4,4-diarnino-diphenyl-rnethane.

4,4'-diamino-diphenyl ether. 1 ,4-dian1ino-2-methyl-benzene. 4,4-diamin0-diphenyl ether. d0 4,4-diamino-diphenyl sulphone. Z-hydroxy-naphthow ac1d-(3)-aml1de 1, l-diamino-haxahydro-benzene.

o. 4,4-diamino-diphenyl-urea- 2,7-diamino-diphenylene-oxide. 4,4-diamino-diphenyl-sulphone. 4,4-diarnino-diphenylrnethane. 4,4-diamino-diphenyl ether.

2,7diamino-naphthalene. 4,4-diamino-diphenyl-urea. 4,4-diamino-diphenyl-sulphone.

1,4-diamino-2-methyl-b enzene. 4,4"diarninodiphenyl-methane. 4,4diarninodiphenyl ether. 2,7-diarninonaphthalene. 1,4diamino-2-methyl benzene- 4,4-diamino-diphenyl ether. 4,4diamino-diphenyl-methane. 1,4-dian1ino-hexahydro-benzene.

4,4-diamino-diphenyl ether 4,4-diamino-diphenyl-methane. 1,3-diamino-2-methyl-benzene. 4,4diamin0-diphenyl ether. 4,4-diamino-dipheuyl-urea. 4,4-diarnino-diphenyl-ureav 1,4-dian1in0-2-methyl-benzene. 4,4diamino-diphenyl-methane. 4,4-diamino diphenyl ether. 1,3-diamino-benzene.

. 4,4-diamino-diphenyl-rnethane. 4,4-diamino-diphenylurea. 1,4-diamino-2-methyl-benzene. 4,4-diamino-diphenyl-methane. 4,4-diamino-diphenyl ether. 1,3-dia1nin0-2-methyl-benzene. 4 ,4diamino-diphenyl-rnethane- .do 4,4'-diarnino-diphenyl-urea. hydroxy-naphtho a id 4,4-diamino-cliphenyl other. 2-hydroxy-naphthoic aeid-(3)-2-toluidide 4,4-diarnino-diphenyl-methane. Z-hydroxy-naphthoic acid-(3)4-cthoxy-anilide .i. 4,4-diamino-diphenyl-sulphone. Z-hydroxy-naphthoic acid-(3)-2-1nethoxy-anilide 4,4-diamin0-diphenyl other.

2-hydroxy-naphthoie acid-(3)-(4-acetylarnino) -anilide 1,4-diamiuo-benzene. .do t t 4,4-diamino-diphenyl.

4,4-diamino-diphenylmetbane. 2,7-diamino-naphthalene. 4,4-diamino-2,2-diehloro-(liphenyl. 4,4-diamino 3,3'-dimethyl-diphenyl.

1,4diarnino-benzene. 4,4-diamino-diphenyl. 4,4-diamino-diphenyhnethane. 4,4-diarnino-2,2-dichloro-diphenyl. 4,4 diamino-3,3 dimethyl-diphenyl. lA-diarnino-benzene.

4,4 diamino-diphenyl. 4,4-diaminddiphenyl-methane.

1,4-diamino-ber1zc11e. 4,4-diarnino-diphenyl. 4Adiamino-diphenyl-methane. lA-diamindbenZene. 4,4-diamino-diphenyl. 4,4diamino-2,2-dichloro-diphenyl.

Z-hydroxy-naphthmo aoid-(3)-2-t0luidide 4,4-diarnino-diphenyl-methane. 2-hydr0xy-naphth0ic acid-(3)-4-ethoxy-anilide 4,4-diarnino-diphenyl-rnethane. Do 4,4-diamino-dlphenyl.

EXAMPLE 12 mixture is then cooled to 5060, the precipitated pig- 65 parts 3-amino-phthalic acid are dissolved in 600 parts diluted hydrochloric acid (5:1) and diazotised at 0-5 with a solution of 25 parts sodium nitrite in 100 f 1 parts Water. a

The diazo solution is coupled With a solution of 100 0 OH parts Z-hydroxy-naphthoic acid-(3)-2-toluidide in 700 parts ethanol, to which a solution of 100 parts caustic 0 soda in 200 parts water has been added and which is C0 C1 cooled to 5-10". The reaction mixture is subsequently stirred at 1015 for 4 hours, adjusted to pH 1-2 by g the addition of 10% hydrochloric acid, the dyestuif is filtered off with suction, washed with Water until free 65 from acid, and dried at 80. 160 parts mono-azo-o-di- CO carboxylic acid are thus obtained.

parts of this rnonoazo-o-dicarboxylic acid or 19 parts of the corresponding monoaZo-o-dicarboxylic anhydride the preparation of which is described in the 70 y following paragraph, are heated in 1000 parts o-dichlorobenzene and parts glacial acetic acid (or in 1000 parts glacial acetic acid) With 5.1 parts 2,2'-dichl0ro-4, NHOC OH 4'-dian1ino-diphenyl at 140150 for 20-30 hours (under reflux, if working in glacial acetic acid). The reaction CH3 ment is filtered 011 with suction, washed With 500 parts chlorobenzene at and dried in a vacuum at 80. The yield is 2022 parts of the red pigment dyestuff of the To prepare the above monoazo-o-dicarboxylic anhydride, 50 parts monoazo-o-dicar-boxylic acid are suspended in 400 parts chlorobenzene, 40 parts acetic anhydride are added, the reaction mixture is heated at 120 for about 2 hours, cooled to 20, the product is are obtained. The dyestuff has very good fastness to lacquer coating and light. Its fastness to migration in polyvinyl chloride is excellent' Because of its excellent thermal stability the pigment can be incorporated into copolymers and grafted polymers of acrylonitrile-butadienefiltered off with suction, washed with 200 parts methanol 5 y in order to remove the acetic anhydride, and dried at EXAMPLE 14 80. 42 parts monoazo-o-dicarboxylic anhydride of M.P. 103 parts of the monoazo dyestuff p p from 332 335. are thus g d d h diazotised 3-amino-phthalic acid and 2-hydroxy-naphthoic The plgment can 6 uce 3 i 10 acid-(3)-4-chloroanilide are heated in 250 parts o-difl monoazo'o'dlcarbqyhc aphydnd? 1S firs-t chlorobenzene and parts glacial acetic acid at 120 for inedlailly prepared by heatmg Wlth glacial acetlc acld 23 hours, 1.08 parts 1,4-diaminobenzene are then added In o'dlchlorpbenzene. abou} 2 hours m the absence and the reaction mixture is kept at 130 for a further 8 of the dlamlne, the dlamine being added only afterwards. hours The pigment is filtered Off with suction at The pigment produced according to the above msmlc 15 washed With 100 parts warm o-dichlorobenzene and dried tions has good to very good Colour strength and fastness in a vacuum. 9.2 parts of the brilliant red disazo dyestuif to lacquer coating, light and migration. It is suitable, of the formula inter alia, for colouring plastics; for example, pigment incorporated into polyvinyl chloride does not migrate into non-coloured polyvinyl chloride at temperatures up 20 NH OO OH to C. and under prolonged stress.

Valuable red pigment dyestuffs are also obtained, when the methods described in this example are applied but, instead of the diazo component, coupling component and diamine there mentioned, the diazo and coupling com- 25 ponents and diamines specified in the following table are V employed, the aminophthalic acids being used in the J form of the free acids or of the anhydrides. 0 2

Diazo component Coupling component Dlamiue 3-amino-phtha1ie acid. 2-hydroxy-naphthoic acid-(3)-(2-toluidine) 4,4-diamino-diphe nyl.

Do do t 3,3-dichloro-4,4-d1amino-dlphenyl.

o 2-hydroxy-naphthoic acid-(3)-(2,5'-dichloro)-anilido 3,3-dimethyl-4,4-diamino-diphenyl.

. 3,3-dimethoxy-4,4-diamino-diphenyl.

. 1,4-diamino-benzene.

4,4-diamino-diphenyl.

2,2-dichloro-4,4-diamino-diphenyl.

3,3 -dichloro-4,4-diamino-diphenyl.

. 1,4-diamino-benzene.

3,3 -dichloro-4,4 -diamino-diphenyl.

3,3 -dimethyl-4,4-diamino-diphenyl.

t 3,3-dimethoxy-4,4-diamir1o-diphenyl.

1,4-diamino-benzene.

1,4-diamlno-benzene.

3,3-dichloro-4,4-d1amino-diphenyl.

3,3"dimethyl-4,4-diamino-diphenyl.

. 4,4-diamino-diphenyl.

2,2 -dichloro-4,4 -diamino-diphenyl.

3,3-dimethyl-4,4-diamino-Cliphenyl.

4,4-diamino-diphenyl.

2,2'-dichloro-4,4-diamino-diphenyl.

3,3dichloro-4,4-dlamino-diphenyl.

3,3-dimethyl-4,4-diamino-diphenyl.

. 4,4-diamino-dlphenyl.

2,2-dichloro-4,4-diamino-diphenyl.

. 3,3-dichloro4,4-diamino-diphenyl.

1,4-diamino-benzene.

4,4-diamino-dlphenyl.

2,2-dichloro-4,4-diamino-dlphenyl. t. 3,3-diehloro-4,4-diamino-diphcny1.

Do do 1,4-diamlno-benzene.

EXAMPLE 13 are obtained. The pigment has excellent fastness to lacquer coating, light and migration. Its thermal stability is also excellent and it can therefore be incorporated into copolymers and grafted polymers of acryolnitrile-butadienestyrene at about 240 without being decomposed.

EXAMPLE 15 90 parts 3-amino-phthalic acid are suspended in 1000 parts water, 500 parts ice and 162 parts concentrated hydrochloric acid are added, and the mixture is diazotised at 0-5 with a solution of 34.5 parts sodium nitrite in 200 parts water.

154 parts 2-hydroxy-naphthoic acid (3) 4 ethoxyanilide are suspended in 300 parts alcohol, a solution of parts caustic soda in 200 parts water is added, 500 parts ice are thrown in, and the above diazo suspension is then introduced in portions at 5-10. When the coupling is completed, the reaction mixture is acidified with semiconcentrated hydrochloric acid, the product is filtered off with suction, washed with water until neutral and dried at 80. The yield of monoazo dyestuff is 218 parts. The dye- 21 stuif is converted into the anhydride by heating it in 1000 parts chlorobenzene with 100 parts acetic anhydride at about 100 for 2 hours. The product is filtered off with suction, washed with light petrol, dried at 80, and 179 parts monoazo-o-dicarboxylic anhydride of MP. 296 298 are obtained.

10.0 parts of the anhydride and 1.84 parts 4,4'-diaminodiphenyl are heated in 500 parts o-dichlorobenzene and 50 parts glacial acetic acid at 130140 for 12 hours, the precipitated pigment is filtered off with suction at 60, Washed with 100 parts o-dichlorobenzene at 50 and 100 parts light petrol, and dried. 9.2 parts of the red disazo dyestuff of the formula are obtained. The pigment has very good fastness to light and lacquer coating.

EXAMPLE 16 10.5 parts of the monazo dyestuff prepared from diazotised 3-amino-phthalic acid and 2-hydroxy-naphthoic acid-(3)-4-ethoxy-anilide are heated in 500 parts chlorobenzene and 50 parts glacial acetic at 120 for 4 hours, 2.12 parts 3,3'-dimethyl-4,4-diamino-diphenyl are then added and the reaction mixture is kept at 130135 for a further 20 hours. The precipitated pigment is filtered oif with suction at about 60, washed with 100 parts warm chlorobenzene and dried in a vacuum at 80 until the weight is constant. 10.8 parts of the brilliant red pigment dyestuif of the formula N:N (I? CH l 3 are obtained.

EXAMPLE 17 21 parts 3-arnino-6-methoxy-phthalic acid are suspended in 250 parts water, 150 parts ice and 35 parts concentrated hydrochloric acid are added and the mixture is diazotised at 0-5 with a solution of 7.0 parts sodium nitrite in 40 parts water.

30 parts 2-hydroxy-naphthoic acid-(3)-2'-methoxyanilide are suspended in 40 parts ethanol, 160 parts of a 10% sodium hydroxide solution and 100 parts ice are added, and the above diazo suspension is introduced in portions at -10". The reaction mixture is subsequently stirred at room temperature for 2 hours, acidified with hydrochloric acid (1:1), the dyestuff is filtered 011 with suction, washed with water until neutral, and dried. Yield: 45 parts monoazo dyestulfs.

10.8 parts of this dyestuif are heated in 250 parts chlorobenzene and 25 parts glacial acetic acid at 110 for 2 hours, 1.08 parts 1,4-diamino-benzene are added and the reaction mixture is kept at 125 for a further hours.

22 The precipitated product is filtered off with suction at 40, washed with parts chlorobenzene at 40, and dried in a vacuum at 60 until the weight is constant. 9.4 parts of the pigment dyestufi of the formula OCH;

| \l a L moo I '2 are obtained.

EXAMPLE 18 11.4 parts of the azo dyestuff prepared from diazotised 3-amino 4-chloro-phthalic acid and 2-hydroxy-naphthoic acid-(3)-[naphthyl-(1)]-amide are heated in 500 parts 0- dichlorobenzene and 50 parts glacial acetic acid at for 2 hours. 1.84 parts 4,4'-diamino'diphenyl are then added and the reaction mixture is kept at 140 for a further 15 hours. The precipitated pigment dyestuff is filtered off with suction at 50, washed with warm o-dichlorobenzene and dried at 80 in a vacuum. Yield: 11.1 parts of the dyestuff of the formula are obtained.

EXAMPLE l9 QNMC on @e Valuable red pigment dyestuffs are also obtained, when the methods described in the above examples are applied but, instead of the diazo components, coupling components and diamines there mentioned, the diazo and coupling components and the diamines specified in the following table are employed, the 3-amino-phthalic acids being used in the form of the free acids or of the anhydrides.

clohexylene; naphthylene and the divalent radicals @-W@ Q- Q wherein B is selected from the group consisting of hydrogen, chloro, and methoxy 2. A dyestutr which is free from sulfonic acid groups and corresponds to the formula and methyl, methoxy, ethoxy and nitro; cyclohexylene; naphthylene and the divalent radicals wherein B is selected from the group consisting of hydrogen, chloro, and methoxy 28 4. The dyestuff of the formula E 5. The dyestufi of the formula @NH-CO 0 N l u (l 2 S s N N N O s U Q U;\ 6. The dyestuif of the formula s s N H C l N-- i HQ N=N 9 /N 7. The dyestuif of the formula 3. The dyestuff of the formula 8. The dyestufi of the formula 011 G mmoQnn-oo OH NH-OC OH I l N: 0

N=N o H A l h! .L

A) 2 9. The dyestuff of the formula LEG-CO-NHQ-NH-OC on I N CH.

29 10. The dyestuff of the formula 1 mmoQ-mz-g 30 12. The dyestufi of the formula H5C20 -NHO(!J OH m l B 2 References Cited UNITED STATES PATENTS 2,933,365 4/1960 Moore 260-152 XR 3,356,672 12/1967 Schefczik 260-152 3,402,166 9/1968 Heckl et a1. 260152 FLOYD DALE HIGEL, Primary Examiner US. Cl. X.R.

s 41, 4; 10622, 23, 288; 117 13s.s, 152; 26037, 41, 41.5, 154, 156, 157, 158, 159, 164, 165,204,205, 519, 563, 570, 57s

Page 1 Column UNITED STATES PATENT OFFICE 16 CERTIFICATE OF CORRECTION Patent No. 3'5l3rl-53 Dat d y 1970 Walter Horstmann et al. Inventor(s) is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Line Error should read g1 NO should read Q should read FORM PO-IOSO (IO-69! Page 2 gatent No.

CERTIFICATE OF CORRECTION May 19, 1970 Dated Inventor(s) Walter Horstmann, et a1.

Column Line It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Error should read ll n should read should read FORM F'O-1D5O (10-69) USCOMM-DC 60376-969 u s, covsmmnn rnnmm: ornc: n o-assau Column UNITED STATES PATENT OFFICE Page 3 CERTIFICATE OF CORRECTION Patent No. 3 I 513 I Dated y 19 r 1970 Inventor) Walter Horstmann, et a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Line Error HCOC should read NOC ll R should read R R 2 2 -O- should read M FORM PO-1OS0 (10-69) USCOMM-DC COSTS-P69 B u s COVUINMNY FIINYINB ornc: |n90-165-114 Page 4 Column UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3

,s13,1s3 Dated May 19, 1970 Inventor(s) Line Walter Horstmann, et al.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

N NH-0C should read e -er should read F ORM PO- 1 050 (10-69) USCOMM-DC 60376-969 Q u 5 covtnuniu'r "mums OFFICE I!" O-Jii-JJJ UNITED STATES PATENT OFFICE Page 5 CERTIFICATE OF CORRECTION Patent 3 ,513 153 Dated May 19 1970 Walter Horstmann, et al. Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column Line Error should read should read FORM PO-IOSO (ID-SQI 

